<p> This thesis describes the ionic strength and ion binding effects on the oxidation reduction properties of cytochrome c and its lysine modified derivatives.</p> <p> Cytochrome c has been modified in two different ways: a complete modification of all lysine residues and specific modification of one lysine residue. Some properties of the modified derivatives are described.</p> <p> Ion binding properties of cytochrome c and its lysine modified derivatives were studied by measuring the apparent equilibrium constant of the reaction between the ferri- form of the protein and potassium ferrocyanide. It was found that unmodified cytochrome c binds one cation (K+, Na+) per molecule, and binding is much stronger to the reduced form of the protein. Binding of cations is not changed upon modification of the lysine residues. For binding of the chloride, there are two binding sites on the cytochrome c molecule, and the binding is much stronger to the oxidized form of the protein. It was shown that upon the modification of the lysine residues in either way the binding of chloride was considerably changed. It was concluded that one of these two binding sites for chloride on cytochrome c involves lysine residue, probably the residue number 13.</p> / Thesis / Master of Science (MSc)

A database is being developed by the NWMO that will be capable of predicting sorption for key elements of interest onto crystalline and sedimentary rocks in the highly saline groundwaters and porewaters at DGR depths in Ontario, Canada. Pd(II), Np(IV), and Np(V) have all been identified as elements of interest by the NWMO. Sorption experiments of Pd(II) were conducted on illite, bentonite, and shale to investigate the effects that ionic strength (I), and pH have on sorption. Na-Ca-Cl solutions ranging from 0.01 – 6.0 M I with pH values between 3 and 9 were considered under aerobic conditions at 25°C for sorption testing conditions. Sorption data for Pd(II), Np(IV), and Np(V) was used with 2SPNE SC and 2SPNE SC/CE models developed in PHREEQC to model sorption onto illite and montmorillonite at different values of I and pH. These models were also used to test proposed reaction constants from various sources in the existing literature, and to establish and propose optimized surface complexation constants of our own. Optimized reaction constants were compared with the LFER to determine its validity across all test conditions. The LFER was found to not adequately describe sorption of Pd(II), Np(IV), or Np(V) on either illite or montmorillonite. The JAEA TDB, R04, and R07 THEREDA were all tested along with the Davies, Debye-Hückel, SIT, and Pitzer computational methods in order to determine their overall accuracy. The JAEA TDB using the SIT computational method was found to not be capable of modelling Np(IV) onto illite or montmorillonite in 4.0 M I. / Thesis / Master of Applied Science (MASc)

Martin Beneš Determination of stability constants of charged cyclodextrin comlexes by capillary electrophoresis Abstract Stability constant characterizes binding interaction between an analyte and complexation agent. These interactions play very important role in separation processes of, in other way undistinguishable, compounds, e.g. enantiomers. The most widely used complexation agents are cyclodextrins. Affinity capillary electrophoresis (ACE) belongs to methods suitable for the determination of stability constants. The stability constant is determined from the dependence of the effective mobility of analyte on the increasing concentration of complexation agent in background electrolyte (BGE). If charged CDs are used, the attention must be paid not only to viscosity of the BGE and to the influence of Joule heating on the temperature in the capillary but also to the increasing ionic strength. The thermodynamic stability constants of R,R- and S,S-hydrobenzoin and R- and S-(3-brom- 2-methyl-1-propanol) with cationic modified β-cyclodextrin: 6-monodeoxy-6-mono(3- hydroxy)propylamino-β-cyclodextrin hydrochlorid (PABCD) were determined by affinity capillary electrophoresis. The average temperature (25řC) of the BGE in the capillary was kept constant. This was achieved by decreasing of the cassette temperature...

Dissolved organic carbon (DOC) plays an important role in the global carbon (C) cycle because increases in aqueous C potentially contribute to rising atmospheric CO2 levels. Over the past few decades, headwater streams of the northern hemisphere have shown increased amounts of DOC coinciding with decreased acid deposition. Although the issue is widely discussed in the literature, a mechanistic link between precipitation composition and stream water DOC has not yet been proposed. In this study, the breakup of soil aggregates is hypothesized as the mechanistic link between reduced acid deposition and DOC increases in surface waters. Specific hypotheses state that soil aggregate dispersion (and the ensuing release of DOC from these aggregates) is driven by a decrease in soil solution ionic strength (IS, decreasing the tendency of flocculation) as well as a shift from divalent to monovalent cations (reducing the propensity for cation bridging) in soil solution. These hypotheses were tested on soil samples collected from several riparian zone and hillslope positions along three flagged transects in the acid-impacted Sleepers River Research Watershed in northeastern Vermont. To determine soil C content by landscape position, samples from transects spanning hilltop to hillslope and riparian area, as well as replicated hillslope and riparian samples (n=40) were analyzed. Aqueous soil extracts simulate the flushing of soils during hydrologic events (e.g. rain or snowmelt) and were used to test the effect of soil solution chemistry on DOC release. Extracts were prepared with solutions of varying IS (0-0.005M) and composition (CaCl2 and NaCl) on replicated soil samples (n=54) and changes in DOC release and aggregate size were monitored. As IS of the extraction solution increased, the amount of DOC in solution decreased, and aggregate size increased. This was presumably due to cations bridging and diffuse double layer effects. This effect was reversed in low ionic strength solutions where DOC release was significantly higher and average aggregate size was smaller. While extraction solution controlled the amount of C liberated, landscape position impacted the quality, but not quantity, of released DOC. This study is the first to propose a mechanistic link observed changes in DOC in surface waters and recovery from acidification and provides initial experimental evidence that soil aggregates indeed play a role in the generation of DOC.

No description available.

Two studies on potential approaches for processing low-salt, low-fat (LSLF) bologna were completed. In study 1, the effects of three factors, namely salt type (sea salt vs. regular NaCl), NaCl concentration (0.75%, 1.00%, 1.25% and 2.00%) and holding of stuffed batter before cooking (cooked immediately (CI) vs. delayed cooking (DC)), on the quality of LSLF bologna were investigated. There was no difference between salt type for most of the parameters measured. The holding factor significantly improved the water holding capacity (WHC) and texture of bologna samples containing 0.75% NaCl, as shown by lower (p<0.05) expressible moisture. However, holding factor did not affect WHC and instrumental texture of samples with 1.00%, 1.25% or 2.00% NaCl. A NaCl level by hold effect (p<0.05) was observed for texture profile analysis (TPA) in which there was significant improvement in the texture of samples containing 0.75% NaCl that were subjected to DC, but no effect at other NaCl levels. Panelists were able to detect the positive effect (p<0.05) of DC on the texture of samples with 0.75% or 1.00% NaCl. This study showed that DC is effective in improving the texture of bologna samples with extremely low NaCl (0.75%) content. The biggest challenge in this first study was the difficult sample handling experienced during slicing. Since bologna is commonly sold as thin slices, the bologna must be firm enough for ease of slicing. The second study focused on improving bologna firmness by the addition of microbial transglutaminase (MTG), known for its functionality as a protein cross-linker, and of flaxseed meal (FSM), known for its excellent water holding capacity. The physico-chemical and sensory characteristics of 12 treatment combinations (0, 0.15% and 0.30% MTG; 0, 0.5%, 1.0% and 1.5% FSM) were determined. In general, results showed that MTG significantly improved the textural quality of bologna, but resulted in a higher purge loss during storage of vacuum packaged slices. On the other hand, FSM significantly reduced the expressible moisture content and purge loss of the product. In terms of product colour, MTG had no effect but FSM when added to the formulation at level as low as 0.5%, affected the colour as determined by both instrumental and sensory evaluation. The overall results of the project indicated that texture in LSLF bologna is not a major issue, since processing conditions and combinations of ingredients can be manipulated to improve texture. The biggest challenge, however, is in the area of flavour – improving the flavour of low-salt processed meats warrants further research.

No description available.

<p>The kinetics for radiation induced dissolution of spent nuclear fuel is a key issue in the safety assessment of a future deep repository. Spent nuclear fuel mainly consists of UO₂ and therefore the release of radionuclides (fission products and actinides) is assumed to be governed by the oxidation and subsequent dissolution of the UO₂ matrix. The process is influenced by the dose rate in the surrounding groundwater (a function of fuel age and burn up) and on the groundwater composition. In this licentiate thesis the effects of HCO₃- (a strong complexing agent for UO2²⁺) and ionic strength on the kinetics of UO₂ oxidation and dissolution of oxidized UO₂ have been studied experimentally.</p><p>The experiments were performed using aqueous UO₂particle suspensions where the oxidant concentration was monitored as a function of reaction time. These reaction systems frequently display first order kinetics. Second order rate constants were obtained by varying the solid UO₂surface area to solution volume ratio and plotting the resulting pseudo first order rate constants against the surface area to solution volume ratio. The oxidants used were H₂O₂(the most important oxidant under deep repository conditions), MnO₄- and IrCl₆^2-. The kinetics was studied as a function of HCO₃- concentration and ionic strength (using NaCl and Na₂SO₄as electrolytes).</p><p>The rate constant for the reaction between H₂O₂ and UO₂ was found to increase linearly with the HCO3- concentration in the range 0-1 mM. Above 1 mM the rate constant is independent of the HCO3- concentration. The HCO₃- concentration independent rate constant is interpreted as being the true rate constant for oxidation of UO₂ by H₂O₂ [(4.4 ± 0.3) x 10-6 m min-1] while the HCO3- concentration dependent rate constant is used to estimate the rate constant for HCO₃- facilitated dissolution of UO₂2+ (oxidized UO₂) [(8.8 ± 0.5) x 10-3 m min-1]. From experiments performed in suspensions free from HCO₃- the rate constant for dissolution of UO₂2+ was also determined [(7 ± 1) x 10^-8mol m^-2 s^-1]. These rate constants are of significant importance for simulation of spent nuclear fuel dissolution.</p><p>The rate constant for the oxidation of UO₂ by H₂O₂ (the HCO₃- concentration independent rate constant) was found to be independent of ionic strength. However, the rate constant for dissolution of oxidized UO₂ displayed ionic strength dependence, namely it increases with increasing ionic strength.</p><p>The HCO₃- concentration and ionic strength dependence for the anionic oxidants is more complex since also the electron transfer process is expected to be ionic strength dependent. Furthermore, the kinetics for the anionic oxidants is more pH sensitive. For both MnO₄- and IrCl₆2- the rate constant for the reaction with UO₂was found to be diffusion controlled at higher HCO3- concentrations (~0.2 M). Both oxidants also displayed ionic strength dependence even though the HCO₃- independent reaction could not be studied exclusively.</p><p>Based on changes in reaction order from first to zeroth order kinetics (which occurs when the UO₂ surface is completely oxidized) in HCO₃- deficient systems the oxidation site density of the UO₂ powder was determined. H₂O₂and IrCl₆2- were used in these experiments giving similar results [(2.1 ± 0.1) x 10-4 and (2.7 ± 0.5) x 10^-4 mol m^-2, respectively].</p>

The sorption behavior of yttrium and the rare earth elements (YREEs) was investigated using a variety of hydroxide precipitates over a range of solution conditions. Experiments with amorphous hydroxides of Al, Ga, and In were conducted at constant pH (~6.0) and constant ionic strength (I = 0.01 M), while YREE sorption by amorphous ferric hydroxide was examined over a range of ionic strength (0.01 M <̲ I <̲ 0.09 M), pH (3.9 <̲ pH <̲ 7.1), carbonate concentration (0 M <̲ [CO32-]T <̲ 150 micro-M), and temperature (10°C <̲ T <̲ 40°C). Sorption results were quantified via distribution coefficients, expressed as ratios of YREE concentrations between the solid and the solution, and normalized to concentrations of the sorptive solid substrate. Distribution coefficient patterns for Al, Ga, and In hydroxides were well correlated with the pattern for YREE hydrolysis. In contrast, amorphous ferric hydroxide developed a distinct pattern that was different than those for Al, Ga, and In precipitates but similar to the pattern predicted for natural marine particles. YREE sorption was shown to be strongly dependent on pH and carbonate concentration, significantly dependent on temperature, and weakly dependent on ionic strength. Distribution coefficients for amorphous ferric hydroxide (iKFe) were used to develop a surface complexation model that contained (i) two equilibrium constants for sorption of free YREE ions (M3+) by surface hydroxyl groups, (ii) one equilibrium constant for sorption of YREE carbonate complexes (MCO3+), (iii) solution complexation constants for YREE carbonates and bicarbonates, (iv) a surface protonation constant for amorphous ferric hydroxide, and (v) enthalpies for M3+ sorption. This quantitative model accurately described (i) an increase in iKFe with increasing pH, (ii) an initial increase in iKFe with increasing carbonate concentration due to sorption of MCO3+, in addition to M3+, (iii) a subsequent decrease in iKFe due to increasing YREE complexation by carbonate ions (especially extensive for the heavy REEs), and (iv) an increase in iKFe with increasing temperature.

Orientador: Teresa Dib Zambon Atvars / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-08T05:02:01Z (GMT). No. of bitstreams: 1 Barros_DavisonStoraide_M.pdf: 2037047 bytes, checksum: bfc81c7ccb14370261c20ba48859e0ec (MD5) Previous issue date: 2006 / Resumo: Neste trabalho são estudadas as propriedades fotoquímicas e morfológicas de filmes automontados compostos de um polieletrólito fraco e azocorantes em função das condições impostas nas soluções de origem, como o pH, a força iônica e tamponamento. Na automontagem, os filmes são fabricados pela deposição de camadas alternadas de dois materiais, de cargas elétricas opostas, a partir de suas soluções aquosas em um substrato de vidro. Os materiais usados foram o polieletrólito catiônico hidrocloreto de poli(alilamina) (PAH) e três azocorantes aniônicos: Vermelho do Congo (CR), Ponceau SS (PSS) e Alaranjado de Metila (MO). Foram fabricados filmes de PAH/CR, PAH/PSS e PAH/MO. Para avaliar somente o efeito do pH, foram usados três valores de pH (3, 7 e 10). Para verificar o efeito da força iônica, foram usadas soluções aquosas de cloreto de potássio em diferentes concentrações e, para verificar a influência de tampão, foram usados três sistemas tampão, um para cada valor de pH. Foram usadas as técnicas de espectroscopia UV-vis e turbidimetria para investigar as propriedades espectroscópicas das soluções, dos filmes e a solubilidade do PAH. Foi utilizada a técnica de microscopia de força atômica para verificar a morfologia do filme. Observa-se que a deposição dos corantes e do PAH no filme depende de suas densidades de carga, bem como da presença de outras espécies iônicas em solução. Tanto um aumento do pH como a presença de contra-íons, leva a uma redução da carga do PAH e causa um aumento de sua adsorção no filme, acompanhado de um aumento de rugosidade superficial. Porém, a primeira condição pode ou não diminuir as cargas dos corantes e a segunda enfraquece a atração eletrostática, reduzindo as suas deposições. As interações do par corante-PAH induzem a agregação dos corantes em solução e nos filmes. As diferenças estruturais dos corantes são igualmente importantes, pois o CR e o PSS são os que mais se depositam e apresentam diferentes comportamentos de deposição em função do pH. Verifica-se também que o PAH interage distintamente com diferentes contra-íons, o que pode ser explicado considerando-se a especificidade iônica e não o simples conceito de força iônica / Abstract: In this work, the photochemical and morphological properties of layer-by-layer self¿assembly films made of a weak polyelectrolyte and azodyes are studied in dependence of the solution¿s pH, ionic strength and buffering. In self-assembly technique, films are made from deposition of alternate layers of two compounds, which have opposite electrical charges, from their solutions onto a glass substrate. We employed the polyelectrolyte poly(allylamine) hydrochloride (PAH) which is positively ionized when in aqueous solution and the three different anionic azodyes: Congo Red (CR), Ponceau SS (PSS) and Methyl Orange (MO). Films of PAH/CR, PAH/PSS and PAH/MO were prepared. To investigate only the pH effect, three pH values were used (3, 7 and 10). To investigate the ionic strength, potassium chloride aqueous solution at different concentrations were used and to verify the buffer effect, three buffer systems were used, one for each pH. The UV-Vis Spectroscopy and Turbidimetry were employed to study the spectroscopic properties of the solutions, films and PAH solubility. The Atomic Force Microscopy was used to verify the film morphology. One observes that the dyes and PAH deposition depend on their charge densities as well the presence of other ionic species. An increase in solution¿s pH and/or the presence of counter-ions reduces PAH¿s charge increasing its adsorption on film, accompanied by a higher surface roughness. Differently, the first condition can or cannot reduce the dye¿s charge and the second weakens the electrostatic interaction, reducing dye adsorption. The pair dye-PAH interactions induces the dye aggregation both in solution and film. The structural differences between dyes are equally important, as CR and PSS are the ones that adsorb most and show different deposition behavior in function of solution¿s pH. Also, one verifies that PAH interacts distinctly with different counter-ions, a fact that can be explained considering ionic specificity and not by the simple concept of ionic strength / Mestrado / Físico-Química / Mestre em Química